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• W2134757709 startingPage "715" @default.
• W2134757709 abstract "Rhodium-catalyzed intramolecular carboacylation of alkenes, achieved using quinolinyl ketones containing tethered alkenes, proceeds via the activation and functionalization of a carbon-carbon single bond. This transformation has been demonstrated using RhCl(PPh(3))(3) and [Rh(C(2)H(4))(2)Cl](2) catalysts. Mechanistic investigations of these systems, including determination of the rate law and kinetic isotope effects, were utilized to identify a change in mechanism with substrate. With each catalyst, the transformation occurs via rate-limiting carbon-carbon bond activation for species with minimal alkene substitution, but alkene insertion becomes rate-limiting for more sterically encumbered substrates. Hammett studies and analysis of a series of substituted analogues provide additional insight into the nature of these turnover-limiting elementary steps of catalysis and the relative energies of the carbon-carbon bond activation and alkene insertion steps." @default.
• W2134757709 created "2016-06-24" @default.
• W2134757709 creator A5017712496 @default.
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• W2134757709 date "2011-12-20" @default.
• W2134757709 modified "2023-10-16" @default.
• W2134757709 title "Rate-Limiting Step of the Rh-Catalyzed Carboacylation of Alkenes: C–C Bond Activation or Migratory Insertion?" @default.
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